WO2007088896A1 - Procede de production de film conducteur, film de protection electromagnetique transmettant la lumiere, filtre optique et ecran plasma - Google Patents

Procede de production de film conducteur, film de protection electromagnetique transmettant la lumiere, filtre optique et ecran plasma Download PDF

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Publication number
WO2007088896A1
WO2007088896A1 PCT/JP2007/051613 JP2007051613W WO2007088896A1 WO 2007088896 A1 WO2007088896 A1 WO 2007088896A1 JP 2007051613 W JP2007051613 W JP 2007051613W WO 2007088896 A1 WO2007088896 A1 WO 2007088896A1
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WIPO (PCT)
Prior art keywords
silver
film
layer
electromagnetic wave
shielding film
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PCT/JP2007/051613
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English (en)
Japanese (ja)
Inventor
Hirotomo Sasaki
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Fujifilm Corporation
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Publication of WO2007088896A1 publication Critical patent/WO2007088896A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel

Definitions

  • the present invention relates to the front surface of a display such as a CRT (cathode ray tube), a PDP (plasma display panel), a liquid crystal, an ELP (electric aperture luminescence panel (also referred to as EL)), or a FED (field emission display).
  • a display such as a CRT (cathode ray tube), a PDP (plasma display panel), a liquid crystal, an ELP (electric aperture luminescence panel (also referred to as EL)), or a FED (field emission display).
  • the present invention relates to an electromagnetic shield that shields electromagnetic waves generated from a microwave oven, electronic equipment, printed wiring board, etc., and in particular, a translucent electromagnetic wave shielding film having translucency, and an optical filter provided with the translucent electromagnetic wave shielding film And plasma display panels.
  • the above-mentioned countermeasure against EMI requires the ability to shield electromagnetic waves.
  • a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, and a method of covering the cable with a metal foil are employed.
  • CRT, PDP, etc. it is necessary for the operator to recognize characters displayed on the screen, so transparency on the display is required. For this reason, any of the above methods is inappropriate as an electromagnetic wave shielding method in which the front surface of the display often becomes opaque.
  • a PDP generates a larger amount of electromagnetic waves than a CRT or the like, and thus a stronger electromagnetic wave shielding ability is required.
  • the electromagnetic wave shielding ability can be simply expressed by the surface resistance value.
  • the surface resistance value is required to be about 300 ⁇ / sq or less.
  • translucent electromagnetic shielding material for 2.5 Q Zsq or less is required, and for consumer plasma televisions using PDP, 1.
  • the required level of transparency is about 70% or more for CRT and 8 for PDP.
  • Visible light transmittance of 0% or more is required, and much higher transparency is desired.
  • Patent Document 1 discloses an electromagnetic shielding material such as a conductive fiber cover.
  • this shield material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and it is difficult to see the characters displayed on the display.
  • Patent Documents 5 to 8 There has been proposed a method of forming a metal thin film mesh on a transparent substrate by an etching process using a photolithography method. Since this method allows fine processing, it has the advantage that a mesh having a high aperture ratio (high transmittance) can be created and can be shielded even when strong electromagnetic waves are emitted. However, the manufacturing process is complicated and complicated, and the production cost is high. Ettin It is known that the intersection of the lattice pattern is thicker than the line width of the straight line part. In addition, the problem of moire was pointed out and improvement was desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-327274
  • Patent Document 2 JP 11 170420 A
  • Patent Document 3 Japanese Patent Laid-Open No. 5-283889
  • Patent Document 4 JP-A-11-170421
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2003-46293
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-23290
  • Patent Document 7 JP-A-5-16281
  • Patent Document 8 Japanese Patent Laid-Open No. 10-338848
  • Patent Document 9 Japanese Unexamined Patent Application Publication No. 2004-207001
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2004-221564
  • Patent Document 10 has advantages such as being able to precisely control the shape of the mesh, imparting high transparency, and enabling mass production at low cost compared to other methods.
  • advantages due to the high resistance of the developed silver conductive mesh, it is difficult to perform direct electroplating, and electroless plating and electroplating are used together when plating on large-area films. There is a need to. Therefore, improvement has been desired due to problems such as deterioration in productivity and high plating costs.
  • the electroplating process is performed by single wafer processing and batch processing.
  • electroplating is performed on a film with a large surface resistance of ⁇ ⁇ / sq or more by single wafer processing
  • the film portion that is in contact with the plating solution is mostly deposited on the portion near the current-carrying side.
  • this phenomenon occurred at the start of plating, that is, at the first power supply, and it was difficult to uniformly apply the plating even if the plating was continued thereafter.
  • a method of printing the above electroless plating catalyst as a grid pattern by a printing method and then performing electroless plating is, for example, when using screen printing, a patterning force screen of a plating catalyst nucleus or an intaglio. This breaks in units of size, resulting in the mesh breaking.
  • a photolithography method is used, the mesh breaks in units of exposure mask size. The reason for this is that since the exposure method is a single-wafer photomask, the exposure to the exposed photoresist is long, and the entire roll film cannot be exposed continuously, and exposure within the photomask size range is possible. This must be repeated once.
  • near infrared cut performance is an important required characteristic for the purpose of preventing malfunction of the remote control.
  • the generation of near-infrared light has increased with the increase in PDP brightness.
  • Cutting performance is required.
  • the film or functional film having the antireflection function is also supplied as a roll-like film like the film having the near-infrared cut function. Therefore, if the conductive mesh of the electromagnetic wave shielding film is interrupted, the material is lost. There was a problem of doing.
  • the means for imparting the electromagnetic wave shielding function to the PDP is an optical for PDP having a base material such as glass, plastic sheet, or plastic film, in which the electromagnetic wave shielding film is bonded to the image display panel using an adhesive.
  • a method such as attaching an electromagnetic shielding film to the filter is used.
  • an adhesive is used.
  • a photographic film has been very rarely used for bonding to glass or plastic with such an adhesive.
  • the support surface conventionally used in photographic film is bonded to glass, the peel strength of the bonded surface is insufficient and peeling occurs over time.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to improve the productivity with a small loss of the shielding material, and to form a continuous mesh pattern in a large amount at a low cost. It is to provide a shielding film.
  • a second object is to provide an electromagnetic wave shielding film having excellent adhesion (peeling strength) to an glass shielding substrate or the like of an electromagnetic wave shielding film obtained from a photosensitive material.
  • a further object of the present invention is to provide a light-sensitive material having an easy-adhesion layer in which developed silver is not substantially formed in an unexposed portion on a conductive film obtained by developing the light-sensitive material, that is, no capri is formed. And it is providing an electromagnetic wave shielding film.
  • another object of the present invention is to provide a translucent electromagnetic shielding film having both high electromagnetic shielding properties and high near-infrared cut performance.
  • Another object of the present invention is to provide an optical filter and a plasma display having high electromagnetic shielding properties and high near infrared cut performance.
  • the first method for producing a conductive film of the present invention is a method for producing a conductive film comprising a developing step of exposing and developing a photosensitive film having a silver salt emulsion layer containing a silver salt on a support.
  • the reduction process process which makes a reducing agent contact the surface of the said photosensitive film, and the smoothness process process which smoothes the said photosensitive film.
  • the reduction process may be performed after the smoothing process or the smoothing process may be performed after the reduction process.
  • the second method for producing a conductive film of the present invention includes a step of exposing a photosensitive film having a silver salt emulsion layer containing a silver salt on a support to develop a metallic silver portion by developing.
  • a smoothing treatment step of smoothing the photosensitive film subjected to the reduction treatment According to the first and second methods for producing a conductive film of the present invention, the electrical resistance of the obtained conductive film can be reduced.
  • a conductive metal such as metallic silver or copper formed by electrolytic plating
  • the manufacturing method of the present invention only the reduction treatment may be performed without performing the smoothing treatment, but the electrical resistance of the conductive film can be reduced by using the smoothing treatment and the reduction treatment in combination. It can be sufficiently reduced.
  • the smoothing process is a calendar process
  • the calendar process is a linear pressure of 1960 N / cm (200 kgf / cm) or more. Is preferably carried out.
  • the reducing agent is an alkaline aqueous solution, and the reducing agent is sodium triacetoxyborohydride, dimethylamine borane or sodium borohydride. Preferably there is.
  • the metal silver part preferably contains 50 to: LO 0% by mass of Ag.
  • the physical image and / or the staking process may not be substantially applied to the metal silver part.
  • the electrolytic plating process may further include an electrolytic plating process in which the metallic silver part is subjected to an electrolytic plating process. It is preferable to be used.
  • the metallic silver portion is treated with a silver ion ligand instead of the reduction treatment or in addition to the reduction treatment. By performing this treatment, the electrical resistance can be further sufficiently reduced.
  • the present invention is a translucent electromagnetic shielding film formed by forming a mesh-shaped metallic silver portion on a support, wherein the mesh-shaped metallic silver portion contains 50 to L00% by mass of Ag.
  • a metallic silver portion in which metallic silver wires having a line width of 18 ⁇ m or less are combined in a mesh shape with an aperture ratio of 85% or more, and the shield film has a surface resistance of 5 ⁇ / sq or less
  • a translucent electromagnetic wave sheet characterized in that it is a shield film in which the mesh-shaped metallic silver portion is continuous for 3 m or more in the longitudinal direction and the mesh-shaped metallic silver portion is disconnected at 10 locations / m 2 or less. It is also in the film.
  • the translucent electromagnetic wave shielding film preferably has a haze generated by light transmission of 10% or less.
  • Such a translucent electromagnetic wave shielding film can be manufactured using the conductive film manufactured by the manufacturing method of the first and second conductive films of the present invention.
  • the present invention also provides a light-transmitting electromagnetic wave shielding film for a plasma display panel, an optical filter, or a plasma display manufactured using the light-transmitting electromagnetic wave shielding film. There is also a play panel.
  • the present invention may be in the following forms.
  • a translucent electromagnetic wave shielding film in which a mesh-shaped metallic silver portion is formed on a support, wherein the mesh-shaped metallic silver portion has a line width of 18 m containing 50 to Ag LOO.
  • the following metallic silver wire is a metallic silver part that is combined in a mesh shape with an aperture ratio of 85% or more, and the shield film has a surface resistance value of 5 ⁇ / sq or less, and the mesh-like shape in the longitudinal direction.
  • a translucent electromagnetic wave shielding film characterized in that the metallic silver part is a shielding film having a continuous length of 3 m or more, and the mesh-shaped metallic silver part has a break of 10 places / m 2 or less.
  • a translucent electromagnetic wave shielding film for plasma display panels comprising the translucent electromagnetic wave shielding film described in any one of 1) to 9) above.
  • the present invention it is possible to provide a method for producing a conductive film that can sufficiently reduce the electrical resistance of the conductive film. Furthermore, according to the present invention, it is possible to provide a translucent electromagnetic wave shielding film in which a continuous mesh pattern is formed in a large amount at a low cost by improving the productivity with little loss of the shielding material.
  • the electromagnetic wave shielding film excellent in the adhesiveness (peeling strength) to the glass substrate etc. of the electromagnetic wave shielding film obtained from a photosensitive material can be provided.
  • a translucent electromagnetic wave shielding film having excellent productivity, low cost, no generation of capri, and high electromagnetic wave shielding properties, an optical filter and a plasma display panel using the same Can be provided.
  • FIG. 1 is a schematic view showing an example of an electroplating bath suitably used for electroplating treatment.
  • FIG. 2 is a schematic view showing an example of a conductive film obtained by the method for producing a conductive film of the present invention.
  • “mesh” in “continuous mesh pattern” or the like refers to a mesh pattern having a plurality of fine line forces or a net having a plurality of fine line forces according to an example in the art.
  • a continuous mesh pattern is a pattern in which fine lines are not substantially cut (10 locations / m 2 or less) and is continuous over a long distance.
  • High productivity of translucent electromagnetic shielding film because it can be cut at the position.
  • the “conductive film referred to as an electromagnetic wave shielding film when used for electromagnetic wave shielding”
  • it is not connected to other components (component film) to be laminated. As long as there is no confusion, it is sometimes called “electromagnetic wave shielding film” or simply “film”.
  • the thickness of the support in the translucent electromagnetic wave shielding film of the present invention is 200 m or less, preferably 20 to 180 / ⁇ ⁇ , more preferably 50 to 120 m. If it is in the range of 10 to 200 m, a desired visible light transmittance can be obtained, and handling is easy.
  • the method for forming the metallic silver portion is not particularly limited, but a photosensitive material containing a silver salt (film-like) In the case of being processed, it is most advantageous to form the photosensitive film) by a developing method. Therefore, the following description explains the case where a method of developing a photosensitive material containing a silver salt is adopted.
  • the thickness of the metallic silver portion can be appropriately determined according to the coating thickness of the silver salt-containing layer coating (silver salt emulsion) coated on the support.
  • the thickness of the metallic silver part is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 0.01 to 9 ⁇ m. Most preferred is ⁇ 5 / ⁇ ⁇ .
  • a metallic silver part is pattern shape.
  • the metallic silver part may be a single layer or a multilayer structure of two or more layers.
  • different color sensitivities can be imparted so that it can be exposed to different wavelengths.
  • different patterns can be formed in each layer.
  • the translucent electromagnetic shielding film including the patterned metal silver portion having a multilayer structure formed as described above can be used as a high-density printed wiring board.
  • the thickness of the metallic silver part is preferable for use as an electromagnetic wave shielding film of a display because the viewing angle of the display becomes wider as it is thinner.
  • the thickness of the metallic silver part is preferably less than 9 ⁇ m, more preferably 0.1 m or more and less than 5 ⁇ m, and more preferably 0.3 or more and less than 3 m. More preferably.
  • a metal silver portion having a desired thickness is formed by controlling the coating thickness of the above-described silver salt-containing layer, and the thickness of the layer made of conductive metal particles is further reduced by physical development and Z or staking treatment. Since it can be freely controlled, even a translucent electromagnetic shielding film having a thickness of less than 5 ⁇ m, preferably less than 3 ⁇ m can be easily formed.
  • the present invention supports a pattern containing a necessary amount of conductive metal. Since it can be provided on the body, it is sufficient to use only the minimum amount of metal, which is advantageous in terms of both reducing manufacturing costs and reducing the amount of metal waste.
  • FIG. 2 shows an example of the conductive film of the present invention.
  • a conductive film 21 shown in FIG. 2 has a conductive functional layer 22 on a support 23.
  • the conductive functional layer 22 contains a silver halide emulsion layer 28.
  • a metal silver portion can be formed by performing exposure 'development processing or the like on the exposed portion 24, and a conductive metal portion can be formed by applying electrolytic plating in order to further increase the conductivity.
  • the unexposed part 25 becomes a light-transmitting part (for example, made of gelatin).
  • the preferred adhesive layer of the present invention will be described.
  • the easy adhesion layer is composed of one layer, and may be composed of two or more layers.
  • an easy-adhesion layer having the following two-layer structure on the surface of the support on which the metallic silver portion is not provided.
  • Antistatic layer comprising water-dispersible or water-soluble synthetic resin, carpositimide compound and conductive metal oxide particles as essential components
  • Second layer Surface layer containing water-dispersible or water-soluble synthetic resin and cross-linking agent as essential components (It is not the surface layer when laminated with other constituent layers, but it means the top layer of the easy-adhesion layer)
  • the easy adhesion layer is provided with an antistatic layer and a surface layer in this order on a support.
  • the haze of the low charge support obtained by providing the antistatic layer on the support is 3% or less, and the surface electrical resistance of the surface layer of the resulting photosensitive material
  • the conductivity is imparted so that is in the range of 8 X 10 6 to 6 ⁇ 10 8 ⁇ .
  • the haze in the present specification is a value measured according to JIS K-7105 using a haze meter (NDH2000, Nippon Denshoku) under the measurement conditions of 25 ° C. and 60% RH.
  • the antistatic layer is a layer containing conductive metal oxide particles, and generally further contains a binder.
  • the conductive metal oxide particles are preferably needle-like particles having a major axis to minor axis ratio (major axis Z minor axis) in the range of 3 to 50. . In particular, those having a major axis Z minor axis in the range of 10 to 50 are preferred.
  • the minor axis of such acicular particles is preferably in the range of 0.001 to 0.0, and particularly preferably in the range of 0.01 to 0.02 / zm.
  • the major axis is preferably in the range of 0.1 to 5. O / zm, and particularly preferably in the range of 0.1 to 2. O / zm.
  • Materials for the conductive metal oxide particles include ZnO, TiO2, SnO, AlO, InO.
  • metal oxides containing different atoms can be mentioned.
  • SnO metal oxide
  • ZnO, A10, TiO, InO, and MgO are preferred and SnO, ZnO, InO and
  • SnO is particularly preferred, with 2 3 2 2 3 2 2 2 and TiO being preferred.
  • TiO is particularly preferred.
  • ZnO is particularly preferred, with 2 3 2 2 3 2 2 2 and TiO being preferred.
  • ZnO is particularly preferred.
  • the material of the conductive metal oxide particles is preferably a material containing a small amount of different elements with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure. Examples of the conductive metal oxide particles containing a small amount of different atoms include SnO doped with antimony.
  • antimony-doped SnO having the dimensions of the short axis and the long axis
  • the use of 2 metal oxide particles is advantageous for forming an antistatic layer that is transparent and has good electrical conductivity. As a result, it is possible to easily obtain a light-sensitive material having a low chargeable support having a haze of 3% or less and having a surface electrical resistance of 8 ⁇ 10 6 to 6 ⁇ 10 8 ⁇ . Monkey.
  • acicular metal oxide particles for example, antimony-doped Sn 2 O 3
  • a transparent antistatic layer having good conductivity is advantageously formed.
  • the reasons for this can be considered as follows.
  • the acicular metal oxide particles extend long in the antistatic layer with the long axis direction parallel to the surface of the antistatic layer. It occupies only the length of the short axis diameter in the thickness direction. Since such needle-like metal oxide particles are long in the long axis direction as described above, high conductivity can be obtained even in a small amount that is easy to contact with each other compared to normal spherical particles. . Therefore, the surface electrical resistance can be reduced without impairing transparency.
  • the minor axis diameter is usually smaller than or substantially the same as the thickness of the antistatic layer, and even if it protrudes slightly on the surface, the protruding portion does not protrude. Since it is weak, it is almost completely covered by the surface layer provided on the antistatic layer. Therefore, it is possible to obtain an advantage that there is almost no occurrence of powder falling which is a detachment of the protruding portion from the layer during the conveyance of the support for preparing the photosensitive material, the photosensitive material for exposure and development.
  • the change in surface electrical resistance before and after the development of the photosensitive material is extremely small when the above-mentioned acicular metal oxide is used, compared to the relatively large case of spherical particles, especially after development processing. It can also be said that the transportability is significantly improved. This is presumably because in the case of spherical particles, the arrangement and state of the particles change due to swelling and shrinkage of the film due to the development process, and the number of parts in contact with each other decreases. .
  • the antistatic layer in the present invention generally contains a binder for dispersing and supporting the conductive metal oxide particles.
  • a binder material various polymers such as acrylic resin, bulle resin, polyurethane resin, and polyester resin can be used. From the viewpoint of preventing powder falling, a cured product of a polymer (preferably acrylic resin, vinyl resin, polyurethane resin or polyester resin) and a carpositimide compound is preferable.
  • a polymer and a carboxyimide compound in a water-dispersed state such as a water-soluble one or an emulsion. .
  • the polymer has a methylol group, a hydroxyl group, a carboxyl group, or an amino group so that a cross-linking reaction with the carpositimide compound is possible.
  • a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred.
  • the content of the hydroxyl group or carboxyl group in the polymer is preferably from 0.0001 to L equivalent Zlkg, particularly preferably from 0.001 to L equivalent Zlkg.
  • Acrylic resin includes acrylic acid esters such as acrylic acid and alkyl acrylate, and methacrylic acid esters such as acrylamide, acrylonitrile, methacrylic acid, and alkyl methacrylate.
  • acrylic acid esters such as acrylic acid and alkyl acrylate
  • methacrylic acid esters such as acrylamide, acrylonitrile, methacrylic acid, and alkyl methacrylate.
  • examples include stears, methacrylamides, and meta-tallow-tolyl homopolymers of any of the monomers, or copolymers obtained by polymerization of two or more of these monomers.
  • homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers. Is preferred.
  • the acrylic resin has, as a main component, a monomer having any group of, for example, a methylol group, a hydroxyl group, a carboxy group, and an amino group so that a crosslinking reaction with a carpositimide compound is possible. Is a polymer obtained by partially using
  • Examples of the above-mentioned bur resin include polybulu alcohol, acid-modified polyvinyl alcohol, polyvinyl enore mannole, polybutyral, polybulu methyl ether, polyolefin, ethylene Z butadiene copolymer, polyacetate bur, chloride.
  • Mention of vinyl Z vinyl acetate copolymer, vinyl chloride Z (meth) acrylate copolymer and ethylene Z acetate butyl copolymer (preferably ethylene Z vinyl acetate Z (meth) acrylate copolymer) Can do.
  • polybulal alcohol, acid-modified polybulal alcohol, polybullymarl, polyolefin, ethylene z butadiene copolymer and ethylene Z butyl acetate copolymer (preferably ethylene Z butyl acetate Z acrylic) Acid ester copolymers) are preferred.
  • the above-mentioned vinyl resin is capable of crosslinking reaction with a carposimide compound, such as polybulal alcohol, acid-modified polyvinyl alcohol, polybul formal, polybulutyl, polybulumethyl ether and polyacetate butyl.
  • a polymer having a hydroxyl group is obtained by leaving an alcohol unit in the polymer.
  • a part of a monomer having a methylol group, a hydroxyl group, a carboxyl group, or an amino group is used for crosslinking.
  • a possible polymer is used for crosslinking.
  • polyurethane resin examples include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), polyhydroxy compounds and polybasic compounds.
  • the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carpositimide compound.
  • the polyester resin generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid.
  • a polyhydroxy compound eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane
  • the polyester resin for example, after the reaction between the polyol and the polybasic acid is completed, the unreacted hydroxyl group and carboxyl group can be used as a functional group capable of a crosslinking reaction with the calpositimide compound.
  • a third component having a functional group such as a hydroxyl group may be added.
  • acrylic resin and polyurethane resin are preferable, and acrylic resin is particularly preferable.
  • calpositimide compound used in the present invention it is preferable to use a compound having a plurality of calpositimide structures in the molecule.
  • Polycarposimide is usually synthesized by a condensation reaction of an organic diisocyanate.
  • the organic group of the organic diisocyanate used for the synthesis of a compound having a plurality of carposimide structures in the molecule is not particularly limited, and either an aromatic group, an aliphatic group, or a mixture thereof can be used.
  • an aliphatic type is particularly preferable from the viewpoint of reactivity.
  • synthetic raw materials organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
  • organic isocyanates aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
  • organic monoisocyanate isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.
  • calpositimide-based compound that can be used in the present invention is also available as a commercial product such as, for example, calpositrite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).
  • the carbodiimide compound is preferably added in an amount of 1 to 200% by mass, more preferably 5 to 100% by mass, based on the binder.
  • the conductive metal oxide particles were dispersed as they are or in a solvent such as water (including a dispersant and a binder as necessary).
  • a solvent such as water (including a dispersant and a binder as necessary).
  • the dispersion is added to an aqueous dispersion or aqueous solution containing the binder (eg, polymer, carpositimide compound and appropriate additive), and mixed (dispersed as necessary) to form an antistatic layer-forming coating solution.
  • the antistatic layer is formed by applying a coating solution for forming the antistatic layer to a surface of a plastic film such as polyester (on the side where no photosensitive layer is provided), such as a dip coating method or an air knife coating.
  • the applied plastic film such as polyester may be before sequential biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching, before re-stretching, or after biaxial stretching.
  • the thickness of the antistatic layer in the present invention is preferably in the range of 0.01 to 1 ⁇ m.
  • a range of 01-0. 2 / zm is preferred. If it is less than 0.01 / zm, it is difficult to apply the coating agent uniformly, so uneven coating occurs immediately on the product: If it exceeds Lm, the antistatic performance and scratch resistance may be inferior. It is preferable that the conductive metal oxide particles are contained in the antistatic layer in a range of 10 to LOOO% by mass with respect to the binder (for example, the total of the above polymer and carpositimide compound). Furthermore, the range of 100-500 mass% is preferable. Less than 10% by mass In such a case, sufficient antistatic properties cannot be obtained, and if it exceeds 1000% by mass, the haze becomes too high.
  • the antistatic layer and the following surface layer may be used in combination with additives such as a matting agent, a surface active agent, and a slipping agent, if necessary.
  • Matting agents include particles of oxides such as silicon oxide, aluminum oxide and magnesium oxide having a particle size of 0.001 to 10 m, and particles of polymers or copolymers such as polymethylmethalate and polystyrene. Can give.
  • Cationic surfactants amphoteric surfactants, nonionic surfactants and the like can be mentioned.
  • slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof, palmitic acid, stearic acid, behenic acid and esters thereof, and silicone compounds. Can be mentioned.
  • a surface layer may be provided on the antistatic layer.
  • the surface layer is provided mainly for providing adhesion with the adhesive layer and assisting the anti-detachment function of the conductive metal oxide particles of the antistatic layer.
  • various materials such as acrylic resin, beer resin, polyurethane resin, and polyester resin can be used as the material for the surface layer, and the polymers described as the binder in the antistatic layer can be used. Is preferred.
  • the cross-linking agent used for the surface layer is preferably an epoxy compound without affecting the photosensitive properties of the photosensitive material layer to be contacted when the roll is removed in the manufacturing process.
  • Examples of the epoxy compound include 1,4 bis (2 ', 3'-epoxypropyloxy) butane, 1,3,5 triglycidyl isocyanurate, 1,3 diglycidinole-5- ( ⁇ -acetoxy-1- ⁇ -oxypropyl) isosinurate, Sorbitol polyglycidyl ethers, polyglyceryl polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerone polyrenoglycenosidinoatenore, 1, 3, 5 triglycidyl (2 hydroxyethyl) isocyanurate, glycerol polyglycerol Epoxy compounds such as ethers and trimethic lip-and-loop polyglycidyl ethers are preferred as specific products such as Denacol ⁇ -521 and EX- 614B (manufactured by Nagase Kasei Kogyo Co., Ltd.).
  • Ethyleneimine compounds methanesulfonic acid ester compounds such as 1,2-di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane and 1,5 di (methanesulfonoxy) pentane Dicyclohexylcarbodiimide and 1 dicyclohexyl 3- (3 trimethylaminopropyl) carbodiimide hydrochloride 2, 5 Isoxazole compounds such as dimethylisoxazole; Inorganic compounds such as chromium alum and chromium acetate; N-carboethoxy-2-isopropoxy 1,2 dihydroquinoline and N- ( 1 Morpholinocarboxy) Dehydrated condensation type peptide reagents such as 4 methyl pyridinium chloride; active ester compounds such as N, N, -adiboyldioxydisuccinimide and N, N, -terephthaloyl
  • the polymer, epoxy compound, and appropriate additives are added to a solvent such as water (including a dispersant and a binder as necessary) and mixed (necessary). Disperse accordingly) to prepare a surface layer coating solution.
  • a solvent such as water (including a dispersant and a binder as necessary) and mixed (necessary). Disperse accordingly) to prepare a surface layer coating solution.
  • the surface layer is formed by a coating method generally well known on the antistatic layer in the present invention, such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, etast. It can be formed by applying the above surface layer coating solution by a rouge coating method or the like.
  • the layer thickness of the surface layer is preferably in the range of 0.01 to 1 / ⁇ ⁇ , and more preferably in the range of 0.01 to 0.2 m. If it is less than 0.01 m, the antistatic layer has insufficient anti-detachment function for the conductive metal oxide particles, and if it exceeds 1 ⁇ m, it is difficult to apply the coating agent uniformly, so it is applied to the product. Unevenness is likely to occur.
  • the adhesive layer preferably used in the present invention will be described.
  • the translucent electromagnetic wave shielding film of the present invention is bonded via an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display panels, or the like.
  • the refractive index of the adhesive used in the present invention is preferably 1.40-1.70. This is related to the refractive index of the adhesive, such as a plastic film used in the present invention, to reduce the difference and prevent the visible light transmittance from being lowered. 40-1.70 is good with little decrease in visible light transmittance.
  • the adhesive used in the present invention is an adhesive that flows by heating or pressurization.
  • the adhesive exhibits fluidity when heated to 200 ° C. or lower or pressurized to 1 kgfZcm 2 (0.098 MPa) or higher. Since it can flow, a translucent electromagnetic wave shielding film (electromagnetic wave shielding adhesive film) provided with an adhesive layer can be bonded to an adherend by lamination or pressure molding, particularly pressure molding. Further, it can be easily bonded to an adherend having a curved surface or a complicated shape.
  • the softening temperature of the adhesive is preferably 200 ° C or lower.
  • the softening temperature of the adhesive layer is preferably 80 ° C or higher because the environment used is usually less than 80 ° C. preferable.
  • the softening temperature is the temperature at which the viscosity is 10 12 boise or less. Usually, at that temperature, flow is observed within a time of 1 to LO seconds.
  • Typical examples of the adhesive that flows by heating or pressurization as described above are mainly the following thermoplastic resins.
  • epoxy acrylate ( ⁇ 1.
  • urethane acrylate, epoxy acrylate, and polyether acrylate are excellent in terms of adhesiveness.
  • epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and aryl.
  • a polymer having a hydroxyl group in the molecule, such as epoxy acrylate, is effective in improving adhesion.
  • the softening temperature of the polymer used as the adhesive is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C in view of processability. On the other hand, it is preferable to use a polymer having a mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same shall apply hereinafter) of 500 or more.
  • the adhesive used in the present invention may contain additives such as diluents, plasticizers, antioxidants, fillers, colorants, ultraviolet absorbers and tackifiers, as necessary.
  • the thickness of the adhesive layer is particularly preferably 10 to 80 m, more preferably 20 to 50 m, more than the thickness of the conductive layer.
  • the difference in the bending rate between the support and the easy-adhesion layer is 0.14 or less.
  • the difference in the bending rate between the support and the easy-adhesion layer is 0.14 or less.
  • Type epoxy resin novolak type epoxy resin, resorcinol type epoxy resin, polyalcohol 'polydaryl alcohol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as cycloaliphatic Nyanogen bisphenol (all with refractive index 1.55-1.60) can be used.
  • polybutene 1.5125
  • acrylic resin is well known as one that hardly changes color over time, and is preferably used in the present invention.
  • acrylic polymers Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used. By blending several types of acrylic polymers with different molecular weights, it is possible to adjust the viscoelasticity of the adhesive to the desired properties.
  • epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate and the like can also be used.
  • Epoxy acrylate and polyether acrylate are particularly excellent in terms of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and aryl alcohol diglycidyl.
  • Ether resorcinol diglycidyl ether, diglycidyl ester adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether Etc.
  • Epoxy acrylate is effective in improving adhesiveness because it has a hydroxyl group in the molecule, and these copolymerized resins can be used in combination of two or more as required.
  • the polymer that is the main component of the adhesive has a mass average molecular weight of 1,000 or more. When the molecular weight is 1,000 or less, the cohesive force of the composition is too low, and the adhesion to the adherend is reduced.
  • Adhesive curing agents include amines such as triethylenetetramine, xylenediamine, diaminodimethane, phthalic anhydride, maleic anhydride, anhydrous dodecylsuccinic acid, anhydrous pyromellitic acid, and anhydrous benzophenone tetracarboxylic acid.
  • Acid anhydrides such as acids, diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more.
  • the addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the amount of addition is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesion.
  • Glue of adhesive used in the present invention You may mix
  • the electromagnetic wave shielding adhesive film having electromagnetic shielding properties and transparency obtained above can be directly attached to a display such as CRT, PDP, liquid crystal, EL, etc., or a plate or sheet such as an acrylic plate or a glass plate. Paste to and use for display. Further, this electromagnetic wave shielding adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring apparatus, measuring apparatus or manufacturing apparatus that generates electromagnetic waves. In addition, it will be installed in the windows of buildings and automobile windows where there is a risk of electromagnetic interference from radio towers and high voltage lines.
  • the metal silver part is preferably provided with a ground wire.
  • the adhesion between the support and the glass plate and the adhesive layer is preferably at least lOgZcm (lONZm) at 80 ° C according to the test method in conformity with IS08225! /. More preferably, it is more preferably 20 g / cm (20 N / m) or more, and particularly preferably 30 g / cm (30 N / m) or more.
  • adhesives that exceed 2000 gZcm (2 kNZm) can be bonded together. It may not be preferable due to difficulty. However, it can be used without problems if no significant problems occur.
  • the adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that the temperature is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable.
  • the adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, it can be regarded as virtually colorless if the adhesive is thin. Similarly, this is not the case when intentionally coloring as described later.
  • Examples of the adhesive having the above properties include acrylic resin, a 1-year-old refin resin, vinyl acetate resin, acrylic copolymer resin, urethane resin, epoxy resin, Examples thereof include a vinyl chloride-based resin, a vinyl chloride-based resin, an ethylene butyl acetate-based resin, a polyamide-based resin, and a polyester-based resin. Of these, acrylic resin is preferred. Even in the case of using the same rosin, it is possible to reduce the amount of the adhesive by synthesizing the adhesive by a method such as lowering the amount of the crosslinking agent, adding a tackifier, or changing the end group of the molecule. It is also possible to improve the performance.
  • the thickness of the adhesive layer is preferably about 5 to 50 ⁇ m.
  • the thickness is preferably reduced within the above range. Specifically, it is about 1-20 / ⁇ ⁇ . However, if the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.
  • the adhesion strength between the translucent electromagnetic shielding film of the present invention and the glass substrate is as follows: It is preferable that
  • the peel strength is preferably 20 N / m or more. Furthermore, it is preferable that the peel strength after a lapse of 72 hours at a temperature of 60 ° C. and a relative humidity of 90% is a peel strength of 20 N / m or more.
  • the translucent electromagnetic shielding film of the present invention preferably exposes a photosensitive material having an emulsion layer containing a photosensitive silver halide salt on a support, By performing development processing, it is obtained by forming a metallic silver portion and a light transmitting portion in the exposed portion and the unexposed portion, respectively. Further, if necessary, the metallic silver portion may be supported with a conductive metal by subjecting the metallic silver portion to physical development and Z or tacking treatment.
  • a photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed on a support and subjected to a development process. However, a photopolymer for photolithography is applied.
  • a shield film can also be produced for the processed photosensitive material.
  • the method for forming a translucent electromagnetic wave shielding film of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
  • a photosensitive silver halide silver-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet that has a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a non-photosensitive image of the metallic silver.
  • the mode (I) is an integrated black-and-white development type, in which metallic silver is formed on the photosensitive material.
  • the resulting developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent staking or physical development process in that it is a filament with a high specific surface.
  • the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby metallic silver is formed on the photosensitive material.
  • This too Type black and white development type Since the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a small specific surface and is spherical.
  • the silver halide silver particles are dissolved and diffused in the unexposed area, and are deposited on the development nuclei on the image receiving sheet to form metallic silver on the image receiving sheet.
  • This is a so-called separate type, in which the image-receiving sheet is used with the photosensitive material force peeled off.
  • the mode of deviation can also be selected as negative development between negative development processing and reversal development processing (in the case of the diffusion transfer method, negative development processing can be performed by using an auto positive photosensitive material as the photosensitive material. Possible).
  • a plastic film, a plastic plate, a glass plate, or the like can be used as the support of the photosensitive material used in the production method of the present invention.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA; Bulu resin such as vinyl and poly vinylidene; other polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin Fats, triacetyl cellulose (TAC), etc. can be used.
  • the plastic film is preferably a polyethylene terephthalate film or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling and cost!
  • the electromagnetic shielding material for a display requires transparency, it is desirable that the support has high transparency.
  • the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%.
  • the plastic film and the plastic plate that are colored to the extent that they do not interfere with the object of the present invention can also be used.
  • the plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.
  • the type thereof is not particularly limited.
  • tempered glass having a tempered layer on the surface.
  • tempered glass can prevent breakage compared to glass that has not been tempered.
  • the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because the broken piece is small and the end face is not sharp even if it is broken.
  • the photosensitive material used may be provided with a protective layer on the emulsion layer described later.
  • the “protective layer” means a layer having a binder force such as gelatin or a polymer material, and is formed on an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. It is preferable that the protective layer is not provided in the case of performing the sticking treatment.
  • the thickness is preferably 0.2 m or less.
  • the formation method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.
  • the light-sensitive material used in the production method of the present invention preferably has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support.
  • the emulsion layer in the present invention may contain a dye, a binder, a solvent and the like as required in addition to the silver salt.
  • the light-sensitive material may contain a dye at least in the emulsion layer.
  • the dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation.
  • the dye may contain a solid disperse dye.
  • Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243.
  • compounds F1 to F34 described in the publication are preferable.
  • (IV-2) to (IV-7) described in the publication are also preferably used.
  • Other dyes that can be used in the present invention include cyanine dyes and pyrylium dyes described in JP-A-3-138640 as dyes in the form of solid fine particles that are decolored during development or fixing. And Aminium dyes.
  • cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acid group described in JP-A-8-245902, and JP-A-8-333519 Lake type cyanine dyes cyanine dyes described in JP-A-1-266536, horopora-type cyanine dyes described in JP-A-3-136038, pyrylium dyes described in JP-A-62-299959, JP-A-7-253639 Polymer-type cyanine dyes described in JP-A No.
  • the dye may contain a water-soluble dye.
  • water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are useful in the present invention.
  • Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584, 609, 1, 177, 429, Japanese Patent Publication Nos. 48-85130, 49-99620, 49-114420, 52-20822, 59-154439, 59-208548, US Patent 2, 27 No. 4, 782, No.
  • the content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like and from the viewpoint of sensitivity reduction due to an increase in the amount of added calories. 1-5 mass% is further more preferable.
  • Examples of the silver salt used in the present invention include inorganic silver salts such as halogenated silver.
  • inorganic silver salts such as halogenated silver.
  • Halogenated silver preferably used in the present invention will be described.
  • halogenated silver for functioning as an optical sensor. It is used in silver salt photographic film, photographic paper, printing plate making film, emulsion mask for photomask, etc. relating to halogenated silver.
  • the technique can also be used in the present invention.
  • the halogen element contained in the silver halide may be chlorine, bromine, iodine, or fluorine, or a combination thereof.
  • halogen silver containing mainly AgCl, AgBr and Agl is preferably used, and halogen silver containing mainly AgBr and AgCl is preferably used.
  • Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used.
  • Silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide are more preferable, and silver chlorobromide and iodochlorobromide containing 50 mol% or more of silver chloride are most preferable.
  • Silver is used.
  • halogenated silver mainly composed of AgBr means silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more.
  • the silver halide silver grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.
  • Silver halide is in the form of a solid grain, and from the viewpoint of image quality of the patterned metal silver layer formed after exposure and development, the average grain size of silver halide silver is 0 in terms of a sphere equivalent diameter. It is preferably 1 to 1000 ⁇ (1 / ⁇ ), more preferably 0.1 to 100 nm, and even more preferably 1 to 50 nm.
  • the spherical equivalent diameter of a halogenated silver particle is a diameter of a particle having a spherical shape and the same volume.
  • the shape of the silver halide grains is not particularly limited.
  • various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, quadrangular flat plate shape, etc.), octahedral shape, tetrahedral shape, etc.
  • the cubic shape and the tetrahedron shape are preferable.
  • the silver halide grains can have a uniform internal and surface layer, or they can be different. Moreover, you may have the localized layer from which a halogen composition differs in a particle
  • Halogen silver emulsion used as an emulsion layer coating solution for use in the present invention is P. Glalkides, Chimie et Physique Photographique (Paul Montel, 1967), GF Dufin, Pho tographic Emulsion Chemistry (The Forcal Press , 1966), VLZelikman MATSUKI, Managing and Coating Photographic Emulsion (published by The ForcalPress, 1964) and the like.
  • the silver halide emulsion may be prepared by any of an acidic method and a neutral method, and a method of reacting a soluble silver salt with a soluble halogen salt may be a one-side mixing method. Any of a simultaneous mixing method, a combination thereof, and the like may be used.
  • a method for forming silver particles a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used.
  • a method of keeping pAg constant in a liquid phase in which halogenated silver is formed that is, a so-called controlled double jet method can be used.
  • halogenated silver solvent such as ammonia, thioether or tetrasubstituted thiourea. More preferred as such a method is a tetra-substituted thiourea compound, which is described in JP-A Nos. 53-82408 and 55-77737.
  • Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione.
  • the silver halide emulsion used for the formation of the emulsion layer in the present invention is preferably a monodisperse emulsion ⁇ (standard deviation of grain size) Z (average grain size) ⁇
  • the coefficient of variation represented by X100 is 20% or less, More preferably, it is 15% or less, and most preferably 10% or less.
  • the silver halide silver emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.
  • the halogen silver halide emulsion used in the present invention may contain a metal element belonging to Group VIII or VIIB of the periodic table.
  • a metal element belonging to Group VIII or VIIB of the periodic table in particular, in order to achieve high contrast and low capri, it is preferable to contain rhodium compounds, iridium compounds, ruthenium compounds, iron compounds, osmium compounds and the like.
  • These compounds are compounds having various ligands, and examples of such ligands include pseudohalogen ligands such as cyanide ions, cyanogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, Besides ammonia
  • organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazol, 5-methylthiazole, mercaptoimidazole, etc.), urea, and thiourea.
  • a water-soluble rhodium compound can be used as the rhodium compound.
  • the water-soluble rhodium compounds include rhodium (III) halide compounds, hexachlororhodium (III) complex salts, pentachloroacorodium complex salts, tetrachlorodiacolodium complex salts, hexadium salts.
  • examples include bromorhodium (in) complex salts, hexaminerhodium (III) complex salts, trizalatrdium (III) complex salts, and K Rh Br.
  • rhodium compounds are used by dissolving in water or a suitable solvent, but are generally used in order to stabilize the solution of the rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, Hydrofluoric acid, etc.) or halogenated alkali (eg ⁇
  • iridium compound examples include hexadium mouth iridium complex salts such as K IrCl and K IrCl,
  • Hexabromoiridium complex salts Hexabromoiridium complex salts, hexammine iridium complex salts, pentachloro-trosyl iridium complex salts and the like.
  • ruthenium compound examples include hexaclonal ruthenium, pentachloro-trosyl ruthenium, K [Ru (CN)] and the like.
  • iron compound examples include potassium hexanoate ( ⁇ ) and ferrous thiocyanate.
  • ruthenium compounds and osmium compounds are in the form of water-soluble complex salts described in JP-A 63-2042, JP-A 1-285941, JP-A 2-20852, JP-A 2-20855, and the like.
  • Particularly preferred is a hexacoordination complex represented by the following formula.
  • M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.
  • the counter ion has no significance, and for example, ammonium or alkali metal ions are used.
  • Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.
  • silver halides containing Pd (II) ions and Z or Pd elements can also be preferably used.
  • Pd may be uniformly distributed in the halogen silver halide grains, but is preferably contained in the vicinity of the surface layer of the halogen silver halide grains.
  • Pd is “contained in the vicinity of the surface layer of the silver halide grain” when the surface force of the halogenated silver grain is within 50 nm in the depth direction, and the palladium content is higher than that of the other layers. Means to have a layer.
  • Such halogen silver particles can be prepared by adding Pd during the formation of the halogen silver particles, and after adding silver ions and halogen ions in an amount of 50% or more of the total addition amount, Pd is preferably added. It is also preferable to add Pd (II) ions to the surface of the silver halide silver layer by a method such as addition at the time of post-ripening.
  • Pd-containing halogenated silver particles increase the speed of physical development and electroless plating, increase the production efficiency of the desired electromagnetic shielding material, and contribute to the reduction of production costs.
  • Pd is a well-known force used as an electroless plating catalyst
  • Pd can be unevenly distributed on the surface layer of silver halide grains, so that it is possible to save extremely expensive Pd. .
  • Te content of Pd ions and Z or Pd metal element contained in Harogeni ⁇ is 10- 4-0 of silver halide, with respect to the number of moles of silver. 5 mol / More preferably, it is mol Ag, more preferably 0.01 to 0.3 mol Z mol Ag.
  • Examples of the Pd compound used include PdCl and Na PdCl.
  • chemical sensitization performed with a photographic emulsion can be performed in order to further improve the sensitivity as an optical sensor.
  • chemical sensitization methods sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination.
  • sulfur sensitization method and gold sensitization method sulfur sensitization method and selenium sensitization method and gold sensitization method
  • sulfur sensitization method and tellurium sensitization method sulfur sensitization method and tellurium sensitization method.
  • a combination of a sensitizing method and a gold sensitizing method is preferable.
  • the sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C or higher for a predetermined time.
  • a sulfur sensitizer known compounds can be used.
  • various sulfur compounds such as thiosulfate, thioureas, and thiazoles can be used. , Rhodons, etc. can be used.
  • Preferred sulfur compounds are thiosulfate and thiourea compounds.
  • the selenium sensitizer used for the selenium sensitization known selenium compounds can be used. That is, the selenium sensitization is usually performed by adding unstable and Z or non-unstable selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time.
  • the unstable selenium compound compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. .
  • the tellurium sensitizer used in the tellurium sensitizer is a compound that forms silver telluride, which is presumed to be a sensitization nucleus, on the surface or inside of the silver halide silver grains.
  • the formation rate of tellurite silver in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat.Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No.
  • JP-A-4 204640 4-271341, 4-333043, and 5-303157, Journal • Chemical Society ⁇ ⁇ Chemical 'Communication (J.Chem.So Chem.Com mun.) Page 635 ( 1980), 1102 (1979), 645 (1979), Journal of Chemical Society, Perkin Transaction (J. Chem. So Perkin. Trans.) 1, 21 91 (1980) ), S. Patai, The Chemistry of Organic Selenium and Telluniu m Compounds), 1 ⁇ (1986), 2 ⁇ (1987) can be used.
  • a compound represented by the general formula (IIKIIIXIV) in JP-A-5-313284 is preferred.
  • the conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45. ⁇ 85 ° C.
  • Examples of the noble metal sensitizer include gold, platinum, noradium, iridium and the like, and gold sensitization is particularly preferable.
  • Specific examples of gold sensitizers used for gold sensitization include salt and gold acid, potassium chromate orate, potassium thiothiocyanate, gold sulfide, tiodarcos gold (1), tiomannose gold ( I) and the like, can be used per mole 10- 7 ⁇ _ 2 moles silver halide.
  • a cadmium salt, a sulfite salt, a lead salt, a thallium salt, etc. may coexist in the halogen-silver emulsion used in the present invention in the process of halogen-silver particle formation or physical ripening.
  • reduction sensitization can be used.
  • reduction sensitizer stannic salts, amines, formamidinesulfinic acid, silane compounds, and the like can be used.
  • a thiosulfonic acid compound may be added to the above-described halogenated silver emulsion by the method described in European Patent Publication (EP) 293917.
  • the silver halide emulsion used in the production of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen yarn compositions, crystal habits). Different types, those with different chemical sensitization conditions, and those with different sensitivities) may be used in combination.
  • a binder can be used in the emulsion layer for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support.
  • the binder both a water-insoluble polymer and a water-soluble polymer can be used as a binder.
  • binder examples include polysaccharides such as gelatin, polybutyl alcohol (PVA), polyvinylpyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, Examples include polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.
  • the content of the binder contained in the emulsion layer is not particularly limited, and can be appropriately determined within a range in which dispersibility and adhesion can be exhibited.
  • the content of the binder contained in the silver salt-containing layer in the production method of the present invention can be appropriately determined within a range in which dispersibility and adhesion can be exhibited.
  • the content of noinda in the silver salt-containing layer is 1Z2 to 1Z0.1 in terms of AgZ binder volume ratio. More preferably, it is 1 ⁇ 0.5.
  • the solvent used for forming the emulsion layer is not particularly limited, and examples thereof include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, dimethyl sulfoxide, and the like. Examples thereof include sulfoxides, esters such as ethyl acetate, ethers, and the like, and mixed solvents thereof.
  • the content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass with respect to the total mass of silver salt and binder contained in the emulsion layer, and 50 to 80% by mass. A range is preferred.
  • the emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are preferably hardened with a hardener.
  • inorganic or organic gelatin hardeners can be used alone or in combination.
  • active bur compounds such as 1, 3, 5 triatalyloyl-hexahydro s triazine, bis (bululsulfurylmethyl) ether, ⁇ , N'-methylenebis ([j8- (bululsulfurol) propionamide], etc.) active halogen Compound (2, 4 Dichloro 6 —Hydroxy-trisazine, etc.), mucohalic acids (eg, mucochloric acid), N-strength rubamoylpyridyl-um salt (eg, 1 morpholinocarbolu-pyridyl) methanesulfonate, haloamidi-um salt (1 — (1—Black 1-Pyridinomethylene) pyrrolidinium 2-Naphthalenesulfonate, etc.) can be used alone or in combination.
  • the swelling ratio of the emulsion layer can be arbitrarily controlled by adjusting the addition amount of the hardener in the emulsion layer.
  • the amount of hardener added to the emulsion layer is preferred and the range depends on the storage temperature and humidity of the photosensitive material after addition of the hardener, the storage period, the film pH of the photosensitive material, and the amount of binder contained in the photosensitive material. It ’s not clear.
  • the hardener since the hardener can diffuse over all layers located on the same side of the light-sensitive material before reacting with the binder, the hardener is preferably added to the same surface of the photosensitive material including the emulsion layer. Depends on the total binder amount on the side.
  • the preferable hardener content of the light-sensitive material of the present invention is in the range of 0.2 to 15% by weight, more preferably, based on the total binder amount on the same side of the light-sensitive material including the emulsion layer. It is in the range of 0.5 mass% to 6 mass%.
  • the hardener can diffuse, so the hardener should be added to the emulsion layer.
  • it can be preferably added to any layer on the same side as the emulsion layer, and it is also preferable to add it divided into multiple layers.
  • an irradiated part is on a pattern or a non-irradiated part is patterned (inverted).
  • Perform exposure The exposure can be performed using electromagnetic waves. Examples of electromagnetic waves include light such as visible light and ultraviolet light, and radiation such as X-rays. Further, a light source having a specific wavelength may be used for exposure, or a light source having a wavelength distribution may be used.
  • the light source various light emitters that emit light in the visible spectrum region are used as necessary.
  • a red light emitter, a green light emitter, and a blue light emitter are used in combination.
  • the spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used.
  • a cathode ray tube that emits white light by mixing these light emitters is often used.
  • mercury lamp g-line, mercury lamp i-line, etc. which are also preferred for ultraviolet lamps, are used.
  • the exposure in the present invention is a second harmonic light source (SHG) that combines a solid-state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a semiconductor laser as an excitation light source and a nonlinear optical crystal.
  • SHG second harmonic light source
  • a scanning exposure method using monochromatic high-density light such as) can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used.
  • exposure is more preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal.
  • SHG second harmonic generation light source
  • exposure is most preferably performed using a semiconductor laser.
  • the exposure energy is preferably lmj / cm 2 or less, preferably 100 j / cm 2 or less, more preferably 50 j / cm 2 or less. Further preferred.
  • laser light sources include blue semiconductor lasers with a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics-related Conference in March 2001), semiconductor lasers (oscillation) LiNbO SH with a waveguide inversion domain structure
  • Approx. 530nm green laser, wavelength 685nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength 650nm red semiconductor laser (Hitachi type No. HL6501MG), etc., are preferably used. It is done.
  • the method of exposing the silver salt-containing layer in a pattern is preferably scanning exposure using a laser beam.
  • the capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferred.
  • DMD described in Japanese Patent Application Laid-Open No. 2004-1244 is used instead of beam scanning by rotating a polygon mirror. It is also preferable to use it for a light beam scanning system.
  • the development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like.
  • the developer is not particularly limited, but PQ developer, MQ developer, MAA developer, etc. can also be used, and commercially available products such as CN-16, CR-56, CP45X Each developer such as FD-3, Papitor, KODAK prescription C-41, E-6, RA-4, D-19, D-72, or the developer included in those kits should be used. it can. You can also use lith developer.
  • a metallic silver portion preferably a butter-shaped metallic silver portion is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.
  • a dihydroxybenzene developing agent can be used as the developer.
  • Dihydroxybenzene developing agents include hydroquinone, black mouth hydroquinone, isopropyl hydroquinone, methyl hydroquinone, hide mouth quinone monos Forces such as sulfonates Particularly preferred is hydroquinone.
  • auxiliary developing agents that exhibit superadditivity with the above-mentioned dihydroxybenzene-based developing agents include 1-phenol, 1-virazolidone, and paminophenols.
  • a combination of a dihydroxybenzene developing agent and 1-phenolino bisazolidone; or a combination of a dihydroxybenzene developing agent and p-aminophenols is preferably used.
  • 1-phenol 3- virazolidone As the developing agent used in combination with 1-phenol 3- virazolidone or its derivatives used as an auxiliary developing agent, specifically, 1-phenol 3- virazolidone, 1-phenyl 1, 4, 4 Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-1-3-azolidone.
  • P-aminophenol auxiliary developing agents examples include N-methyl p-aminophenol, ⁇ -aminophenol, N— (j8-hydroxyethyl) p-aminophenol, and N— (4-hydroxyphenol) glycine. Of these, N-methyl-paminophenol is preferred.
  • the dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter, but in the present invention, it is particularly preferably used in an amount of 0.23 mol Z liter or more. More preferably, it is in the range of 0.23 to 0.6 mol Z liter.
  • the former is 0.23 to 0.6 mol / liter, more preferably 0.23 to 0.5 mol Z. Liters, the latter is less than 0.06 mol Z liters, more preferred ⁇ 0.03 Monore / Lit Nore ⁇ 0.03 Monore / Lit Nore for use in amounts!
  • the pH increase is 0.5 or less when 1 mol of sodium hydroxide is added.
  • the method of imparting the above properties to the development initiator and the development replenisher is preferably a method using a buffer.
  • the buffer include carbonates, boric acid described in JP-A-62-186259, saccharides (for example, saccharose), oximes (for example, acetooxime), phenols described in JP-A-60-93433.
  • 5-sulfosalicylic acid), triphosphate (for example, sodium salt, potassium salt) and the like can be used, and carbonate and boric acid are preferably used.
  • the amount of the above-mentioned buffering agent (particularly carbonate) is preferably 0.25 monolet / litnore or more, 0.25 ⁇ : L5 monole / litnore power is particularly preferred! / ⁇ .
  • the pH of the development initiator is 9.0 to 11.0, particularly preferably 9.5 to 10.7.
  • the pH of the developer replenisher and the developer in the developer tank during continuous processing are also in this range.
  • the alkali agent used for setting the pH usual water-soluble inorganic alkali metal salts (for example, sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate) can be used.
  • the content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml.
  • the development replenisher may have the same composition as the development starter, and the components consumed in development may have a higher concentration than the starter.
  • additives usually used for the developer used for developing the light-sensitive material in the present invention (hereinafter, both the development initiator and the development replenisher may be simply referred to as "developer") (For example, a preservative and a chelating agent) can be contained.
  • the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite.
  • the sulfite is preferably used in an amount of 0.20 mol Z liters or more, more preferably 0.3 mol Z liters or more.
  • the upper limit is 1. 2 mol Z liter is desirable. Particularly preferred is 0.35 to 0.7 mole Z liter.
  • a small amount of ascorbic acid derivative may be used in combination with sulfite as a preservative for the dihydroxy base BR developer.
  • the ascorbic acid derivative includes ascorbic acid and its stereoisomer erythorbic acid and its alkali metal salts (sodium and potassium salts).
  • sodium erythorbate is preferred in terms of material cost.
  • the amount of the ascorbic acid derivative added is preferably in the range of 0.03-0.12 in terms of mono-ktt, particularly preferably in the range of 0.05-5.10 with respect to the dihydroxybenzene developing agent.
  • the developer does not contain a boron compound.
  • additives that can be used in the developer include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide. ; Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof, and mercapto compounds, indazole compounds, benzotriazole compounds, and benzoimidazole compounds as capri-protecting agents Alternatively, it may be included as a black pepper inhibitor.
  • development inhibitors such as sodium bromide and potassium bromide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide.
  • Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof, and mercapto compounds, indazole compounds, benzotriazole compounds, and benzoimidazole compounds as capri-protecting agents
  • benzoimidazole compound examples include 5--troindazole, 5-p-trobenzoylaminoindazole, 1-methyl-5-troindazole, 6-toluindazole, 3-methyl-5--.
  • the content of these benzoimidazole compounds is usually from 0.01 to LOmmol, more preferably from 0.1 to 2mmol per liter of developer.
  • organic / inorganic chelating agents can be used in combination in the developer.
  • Examples of the inorganic chelating agent that can be used include sodium tetrapolyphosphate and sodium hexametaphosphate.
  • organic chelating agent organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
  • organic carboxylic acids examples include acrylic acid, oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, succinic acid, ashellaic acid, sebacic acid, nonanedicarboxylic acid, decandi power norlevonic acid, undecandi power norlevonic acid. , Maleic acid, itaconic acid, malic acid , Citrate, tartaric acid, and the like, but are not limited thereto.
  • aminopolycarboxylic acids examples include iminoacetic acid, ditrimethyl triacetic acid, ditrimethyl tripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediammine tetraacetic acid, glycol ether tetraacetic acid, 1, 2-Diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and other JP-A-52-25632, 55-67747, 57-
  • JP-A-52-25632 Japanese Patent No. 102624 and Japanese Patent Publication No. 53-40900
  • organic phosphonic acid examples include hydroxyalkylidene-diphosphonic acid and research disclosure (Research Disclosure No. 1) described in US Patent Nos. 3214454 and 3794591 and West German Patent Publication 2227639. 181, Item 18170 ( May 1979), and the like.
  • aminophosphonic acid examples include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like.
  • aminotris methylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid examples include aminotrimethylenephosphonic acid and the like.
  • organic phosphonocanolevonic acids examples include JP-A 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241. Nos. 55-65 955, 55-65956, and the above-mentioned Research Disclosure 1 8170. These chelating agents may be used in the form of alkali metal salts or ammonium salts.
  • JP-A-56-24347, JP-B-56-46585, JP-B-62-2849 and JP-A-4-362942 as silver stain preventing agents in the developer. Can be used. Further, compounds described in JP-A-61-267759 can be used as dissolution aids. Furthermore, in the developing solution, if necessary, a color toner, a surfactant, an antifoaming agent, A hardener or the like may be included.
  • the development processing temperature and time are interrelated, and the force determined in relation to the total processing time. Generally, the development temperature is preferably about 20 ° C to about 50 ° C, more preferably 25 to 45 ° C.
  • the development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.
  • the development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion.
  • a fixing process technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like can be used.
  • Preferable components of the fixing solution used in the fixing step include the following.
  • the fixing agent for the fixing solution used in the present invention examples include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is preferred from the viewpoint of fixing speed.
  • Viewpoint power Sodium thiosulfate may be used.
  • the amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol Z liter. Particularly preferred is 0.2 to 1.5 mol Z liter.
  • the fixer may contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing accelerators.
  • surfactant examples include anionic surfactants such as sulfates and sulfones, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. It is done. A known antifoaming agent may be added to the fixing solution.
  • Examples of the wetting agent include alkanolamine and alkylene glycol. I can get lost.
  • Examples of the fixing accelerator include thiourea derivatives described in Japanese Patent Publication Nos. 45-35754, 58-122535, and 58-122536; alcohols having triple bonds in the molecule; Examples include thioether compounds described in US Pat. No. 4126459; mesoionic compounds described in JP-A-4-229860, and compounds described in JP-A-2-44355 may be used.
  • Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citrate, oxalic acid, maleic acid, glycolic acid and adipic acid, boric acid, phosphate and sulfite.
  • Inorganic buffers such as can be used.
  • the pH buffer acetic acid, tartaric acid, and sulfite are preferably used.
  • the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the introduction of the developer, and is preferably 0.01 to: L 0 mol Z liter, more preferably 0.02 to 0.6. Use about mol Z liters.
  • the pH of the fixing solution is preferably 4.0 to 6.5, and particularly preferably 4.5 to 6.0. Further, it is possible to use a compound described in JP-A-64-4739 as the dye elution accelerator.
  • Examples of the hardener in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts.
  • a preferable compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane.
  • the preferred amount of added calories of the above hardener is 0.01 monole to 0.2 monole / lit nore, more preferably 0.03 to 0.08 mol Z liter.
  • the fixing temperature in the fixing step is preferably about 20 ° C to about 50 ° C, more preferably 25 to 45 ° C.
  • the fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds.
  • the replenishing amount of the fixing solution, 600mlZm 2 or less good Mashigu 500MlZm 2 or less and more preferably tool 300MlZm 2 or less is particularly preferred for the process of the photosensitive material.
  • the photosensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment.
  • the washing water amount is usually 20 liters or less per lm 2 of the light-sensitive material, and can be replenished in 3 liters or less (including 0, ie, rinsing with water). For this reason, not only water-saving treatment can be performed, but also the piping for installing the self-supporting machine can be eliminated.
  • a multi-stage countercurrent system for example, two-stage, three-stage, etc.
  • This multi-stage countercurrent system is used in the present invention.
  • the photosensitive material after fixing is gradually stained in the normal direction, that is, stained with the fixing solution! Good water washing is done.
  • various oxidizer additions and filter filtration may be combined to reduce the pollution load, which is a problem when washing with small amounts of water.
  • JP-A-60-235133 a part or all of them can be used for a processing solution having fixing ability as a previous processing step.
  • water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles, which are likely to occur when washing with a small amount of water, and to prevent the processing agent component adhering to the Z or squeeze roller from being transferred to the processed film. Also good.
  • a dye adsorbent described in JP-A-63-163456 may be installed in the washing tank in order to prevent contamination with dyes eluted from the photosensitive material.
  • the compounds described in JP-A-2-201357, JP-A-2-132435, JP-A-1102553, and JP-A No. 46-44446 are disclosed. May be used as the final bath of the light-sensitive material.
  • metal compounds such as ammonia compounds, Bi, A1, fluorescent brighteners, various chelating agents, membrane pH regulators, hardeners, bactericides, fungicides, alkanolamines, A surfactant can also be added.
  • Water used in the water washing or stabilization process is sterilized with tap water, deionized water, halogen, UV germicidal lamps, various oxidizing agents (such as ozone, hydrogen peroxide, and chlorate). It is preferred to use fresh water. Further, washing water containing the compounds described in JP-A-4-39 652 and JP-A-5-241309 may be used.
  • the bath temperature and time in the water washing treatment or stable temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.
  • the electromagnetic wave shielding film of the present invention is preferably obtained in a shape carrying a contact pattern such as a roll shape from the viewpoint of productivity and ease of production of an optical filter, it is advantageous to use a developing machine for rolls. In particular, it is preferable to use a roller conveyance type automatic developing machine.
  • roller-conveying type automatic developing machine is described in US Pat. Nos. 30,257,795, 3,545,971, etc., and is simply referred to as a roller-conveying type automatic developing machine in this specification.
  • the roller transport type automatic processor preferably has four process powers of development, fixing, washing and drying, other processes (for example, stop process) are not excluded, but these four processes are followed. Is most preferred. Further, instead of the washing step, four steps by a stable step may be used.
  • a component obtained by removing water from the composition of the developer or the fixing solution may be supplied in a solid form and dissolved in a predetermined amount of water and used as a developer or a fixing solution.
  • a form of treating agent is called a solid treating agent.
  • powder, tablet, granule, powder, lump or paste is used as the solid processing agent.
  • a preferred form of the above-mentioned treatment agent is the form or tablet described in JP-A-61-259921.
  • the method for producing the tablets is generally described in, for example, the publications of JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent No. 1,213,808.
  • the granule treating agent is a general method described in JP-A-2-109042, JP-A-2-109043, JP-A-3-3935 and JP-A-3-39739. Can be manufactured. Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862 and German Patent 3,733,861. Can be manufactured in a conventional manner.
  • the bulk density of the solid processing agent and in view of its solubility, from 0.5 to 6.
  • a material inert to the reactive material.
  • a method may be employed in which reactive substances are placed in layers so as to form a layer separated by at least one intervening separation layer, a bag that can be vacuum packaged is used as a packaging material, and the bag is evacuated and sealed.
  • inert means that the substances do not react under normal conditions in the package when they are in physical contact with each other, or even if there is any reaction.
  • the inert material may be inert in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials.
  • an inert substance is a substance that is used simultaneously with two reactive substances.
  • hydroquinone and sodium hydroxide in a developer react when they come into direct contact with each other. Therefore, by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging, Can be stored in a knockout.
  • the packaging material for these vacuum packaging materials is an inert plastic film, a bag made from a laminate of plastic material and metal foil.
  • the mass of the metallic silver contained in the exposed area after the development treatment is preferably 80% by mass or more based on the mass of silver contained in the exposed area before the exposure. It is even more preferable that it is at least%. If the mass of silver contained in the exposed part is 50% by mass or more with respect to the mass of V and silver contained in the exposed part before exposure, high conductivity can be obtained.
  • the gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0.
  • the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high.
  • doping of the above-mentioned rhodium ions and iridium ions into the photosensitive halogen silver halide particles can be mentioned.
  • the developed silver thus obtained is preferably treated with a reducing agent or a silver ion ligand, or heated or calendered. By these treatments, the conductivity of developed silver can be increased. These processes may be performed after the development process and the fixing process after the current image process before the fixing process, or may be performed at both times. [0137] The treatment with a reducing agent or silver ion ligand preferably used in the present invention will be described.
  • a reducing agent or a silver ion ligand it is preferable to perform treatment with a reducing agent or a silver ion ligand.
  • a reducing agent it is sufficient if the silver ion can be reduced to metallic silver, for example, thiourea dioxide, Rongalite, sodium chloride (11), sodium borohydride, sodium triacetoxyborono, idide, Examples thereof include trimethylamine borane, triethylamine borane, pyridine borane, and borane. Among these, particularly preferred is sodium triacetoxyborono, idide, dimethylamine borane or sodium borohydride, which is preferred for alkali.
  • Silver ion ligands include chlorine ions, bromine ions, halogen ions such as iodine ions, pseudohalogen ions such as thiocyanate ions, nitrogen-containing heterocyclic compounds such as pyridine and biviridine, sulfite ions, and 1 , 2, 4-Triazolium-3-thiolates (eg, 1, 2, 4-trimethyl-1, 2, 4-triazolium-3-thiolate), 3, 6-dithiaoctane-1, 8 -Thiol ether compounds such as diols.
  • a calendar process preferably used in the present invention that is, a process using a calendar roll will be described.
  • the mesh-shaped metallic silver portion is preferably treated with a calender roll.
  • the conductivity of the mesh-shaped metallic silver portion can be improved, and the electromagnetic shielding performance can be improved.
  • a calendar roll usually consists of one or more pairs of rolls.
  • a plastic roll such as epoxy, polyimide, polyamide, polyimide amide or a metal roll is used. It is particularly preferable to treat with metal rolls.
  • the linear pressure is preferably 1960 N / cm (200 kgf / cm) or more, more preferably 2940 N / cm (300 kgf / cm) or more.
  • the temperature of the calender roll treatment is preferably 10 ° C to 100 ° C, more preferably 10 ° C to 50 ° C.
  • This calendar process can continuously process a roll-like film.
  • the heat treatment preferably used in the present invention is preferably performed at 40 ° C to 250 ° C, more preferably 60 ° C to 200 ° C, and even more preferably 70 ° C to 150 ° C.
  • the time you like It is preferable to heat-treat for 10 seconds to 1 hour, more preferably for 30 seconds to 30 minutes, and even more preferably for 1 minute to 10 minutes. It is good to carry out after development and before electrolytic plating.
  • the conductive metal particles can be supported on the metal silver portion by only one of physical development or staking treatment. Further, the conductive metal particles can be combined by combining physical development and plating treatment. Can also be supported on the metallic silver part.
  • a metal silver part that has been subjected to physical development and Z or staking treatment is referred to as a “conductive metal part”.
  • “Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to precipitate metal particles. This physical phenomenon is used in the manufacture of instant B & W films, instant slide films, printing plates, etc., and the technology can be used in the present invention.
  • the physical development may be performed simultaneously with the development processing after exposure or may be performed separately after the development processing.
  • the plating process uses electroless plating (reduction plating or substitution plating), electrolysis plating, or both electroless plating and electrolytic plating. be able to.
  • the metallic silver portion after the exposure and development treatment can be further treated with an electroless plating solution.
  • an electroless plating solution a method of treating with an aqueous palladium compound solution or a method of treating with a reducing agent and / or a silver ion ligand is preferred.
  • the former is carried out by treating the metallic silver part after exposure and development with a solution containing Pd.
  • Pd may be divalent palladium ion or metal palladium. This treatment can accelerate electroless plating or physical development speed. Electroless plating with noradium is described in detail in the “Electroless plating” section of the Japan Society for the Science and Chemistry Handbook Applied Chemistry.
  • a plating apparatus for suitably carrying out the above-described electroplating treatment exposes the emulsion layer and electrically feeds the sequentially fed film from a feeding reel (not shown) around which the developed film is wound.
  • the film is fed into a plating tank and the film after plating is sequentially wound around a reel for reeling (not shown).
  • Fig. 1 shows an example of an electroplating bath suitably used for the electroplating treatment.
  • the electrolytic plating bath 10 shown in FIG. 1 is capable of continuously plating a long film 16 (the one subjected to the above exposure and development processing).
  • the arrow indicates the transport direction of the film 16.
  • the electrolytic plating bath 10 includes a plating bath 11 for storing a plating solution 15.
  • a pair of anode plates 13 are disposed in parallel in the plating bath 11, and a pair of guide rollers 14 are disposed inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13.
  • the guide roller 14 can be moved in the vertical direction, so that the processing time of the film 16 can be adjusted.
  • a pair of feed rollers (force swords) 12a and 12b for guiding the film 16 to the plating bath 11 and supplying current to the film 16 are rotatably arranged.
  • a liquid draining roller 17 is rotatably disposed below the outlet-side power supply roller 12b.
  • the liquid draining roller 17 and the outlet-side power supply roller 12b are connected to each other.
  • a water spray (not shown) is installed to remove the plating solution from the film.
  • the anode plate 13 is connected to a positive terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 12a and 12b are connected to a negative terminal of the power supply device (not shown). Yes.
  • the feeding roller 12a on the entrance side and the film 16 are in contact with each other.
  • the distance between the bottom of the surface and the plating solution surface (distance La shown in FIG. 1) is preferably 0.5 to 15 cm, more preferably l to 10 cm, and l to 7 cm. More preferably. Further, it is preferable that the distance (distance Lb shown in FIG. 1) between the lowermost part of the surface where the power supply roller 12b on the outlet side and the film 16 are in contact with each other and the liquid surface is 0.5 to 15 cm.
  • the solution 15 is stored in the bath 11.
  • a plating solution containing 30 gZL to 300 gZL of copper sulfate pentahydrate and 30 gZL to 300 gZL of sulfuric acid can be used.
  • nickel plating nickel sulfate, nickel hydrochloride, or the like can be used.
  • additives such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.
  • the film 16 is set in a state where it is wound on a supply reel (not shown), and the film 16 is placed so that the surface on which the film 16 is to be formed comes into contact with the feeding rollers 12a and 12b. It is wound around a conveyance roller (not shown).
  • the surface resistance of the film immediately before electroplating is 1 to: LOOO Q Zsq is preferred 5 to 500 Q Zsq is more preferred Further, the range is 10 to 100 ⁇ Zsq It is.
  • a voltage is applied to the anode plate 13 and the feed rollers 12a and 12b, and the film 16 is conveyed while being in contact with the feed rollers 12a and 12b.
  • Film 16 is introduced into plating bath 11 and dipped in plating solution 15 to form copper plating.
  • the plating solution 15 adhering to the film 16 is wiped off and collected in the plating bath 11. This is repeated in a plurality of electrolytic baths, and finally washed with water, and then wound up on a reeling reel (not shown).
  • the conveyance speed of the film 16 is set in the range of 1 to 30 mZ.
  • the conveying speed of the film 16 is preferably in the range of 1 to: LOmZ, and more preferably in the range of 2 to 5 mZ.
  • the number of electrolytic plating tanks is not particularly limited, but 10 or less, that is, 10 or less is preferable, 2 to 10 is preferable, and 3 to 6 is more preferable.
  • the applied voltage is preferably in the range of 1 to: L00V, and more preferably in the range of 2 to 60V. When a plurality of electrolytic plating tanks are installed, it is preferable to lower the applied voltage of the electrolytic plating tank stepwise.
  • the amount of current on the inlet side of the first tank is preferably 1 to 30 A. 2 to: L0A is more preferable.
  • the feeding rollers 12a and 12b be in contact with the entire surface of the film (80% or more of the contact area is substantially in electrical contact). It is preferable to perform water washing and acid washing before the plating treatment in the electrolytic bath.
  • the treatment solution used for the acid cleaning can be one containing sulfuric acid or the like.
  • the thickness of the conductive metal part to be attached by the electrolytic plating process is preferable because the viewing angle of the display becomes wider as the electromagnetic wave shielding material of the display is thinner. Furthermore, as a use for conductive wiring materials, thinning is required because of the demand for higher density. From this point of view, the thickness of the conductive metal part is preferably less than 9 m, more preferably 0.1 m or more and less than 5 ⁇ m, 0.1 m or more and 3 ⁇ m. More preferably, it is less than.
  • a known electroless plating technique can be used.
  • it can be used for a printed wiring board and the like, and the electroless plating technique can be used.
  • Electrolytic copper plating is preferable.
  • Chemical species contained in the electroless copper plating solution include copper sulfate and copper chloride, as a reducing agent, formalin glyoxylic acid, as a copper ligand, EDTA, triethanolamine, etc.
  • Polyethylene glycol, yellow blood salt, biviridine and the like can be mentioned as additives for improving the smoothness of wrinkles and glazing films.
  • the conductive pattern on the film is preferably continuous (not electrically interrupted). If even a part of the pattern is connected, the conductive pattern may break, and there is a risk that a non-sticky part may be formed in the first electrolytic plating tank or it may become uneven.
  • the plating speed during the plating process can be high-speed plating with a force of 5 ⁇ mZhr or more that can be performed under moderate conditions.
  • various additives such as a ligand such as EDTA can be added to the plating solution and used.
  • the metallic silver portion after the development processing, the physical development and the Z or mating treatment It is preferable to subject the conductive metal part formed by treatment to an oxidation treatment.
  • an oxidation treatment for example, when a metal is slightly deposited on the light transmitting portion, the metal can be removed, and the light transmitting portion can be made almost 100% transparent.
  • the oxidation treatment examples include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be carried out after the emulsion layer exposure and development treatment, or after physical development or staking treatment, and further after the development treatment and after physical development or staking treatment, .
  • a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, etc.
  • a mesh consisting of these geometric shapes which is preferably a combination of (positive) hexagons, (positive) n-gons such as (positive) hexagons, circles, ellipses, stars, etc. It is even better to be in the shape. From the viewpoint of EMI shielding properties, the triangular shape is the most effective force.
  • the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be suitably determined according to the objective.
  • the line width of the thin metal wire of the conductive metal portion needs to be 18 ⁇ m or less in order to ensure conductivity. If the line width exceeds 18 ⁇ m, it is not preferable because both the aperture ratio and mesh size are constrained to a satisfactory level.
  • the line width is preferably 5 to 18 ⁇ m, more preferably 8 to 16 ⁇ m.
  • the line spacing is preferably 50 ⁇ m or more and 500 ⁇ m or less, more preferably 200 ⁇ m or more and 400 ⁇ m or less, and most preferably 250 ⁇ m or more and 350 ⁇ m or less.
  • the conductive metal part in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and more preferably 95% or more from the viewpoint of visible light transmittance. Is most preferable.
  • the open area ratio is the ratio of the portion without fine lines that make up the mesh to the whole, For example, the aperture ratio of a square grid mesh with a line width of 15 / zm and a pitch of 300 m is 90%.
  • the “light transmitting part” in the present invention means a part having transparency other than the conductive metal part in the light transmitting electromagnetic wave shielding film.
  • the transmittance of the light transmissive portion is 90% or more, preferably the transmittance indicated by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. Is 95% or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.
  • the mesh pattern of the conductive metal portion in the present invention is preferably continuous for 3 m or more in the longitudinal direction of the translucent electromagnetic wave shielding film, and the longer the continuous length of the mesh pattern, the more the optical pattern becomes. It can be said that this is a more preferable mode because the loss in producing the filter material can be reduced.
  • the continuous length is long, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness.
  • the following is preferable. It is preferably 100 m or more and 1000 m or less, more preferably 200 m or more and 800 m or less, and most preferably 300 m or more and 500 m or less.
  • the thickness of the support is preferably 200 ⁇ m or less, more preferably 20 ⁇ m or more and 180 ⁇ m or less, and most preferably 50 ⁇ m or more and 120 ⁇ m or less.
  • the scanning method of the light beam is preferably a method of exposing with a linear light source or a rotating polygon mirror arranged in a direction substantially perpendicular to the transport direction.
  • the light beam needs to be intensity-modulated by two or more values, and the straight line is battered as a series of dots. Since the dots are continuous, the edge of the fine line of one dot is stepped, but the thickness of the fine line means the narrowest length of the constricted part.
  • the mesh pattern is preferably inclined by 30 ° to 60 ° with respect to the longitudinal direction of the translucent electromagnetic wave shielding film. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °.
  • the surface resistance value of the translucent electromagnetic wave shielding film of the present invention is required to be 5 Q Zsq or less.
  • a preferable surface resistance value is ⁇ ⁇ / sq or less, and more preferably 0.7 to 0.03 ⁇ Zsq.
  • the disconnection of the metallic silver portion of the translucent electromagnetic wave shielding film of the present invention needs to be 10 locations / m 2 or less. Thereby, conductivity is ensured and an electromagnetic wave shielding function is exhibited. Preferably, it is 4 sites / m 2 or less, more preferably 1 site / m 2 or less.
  • the translucent electromagnetic wave shielding film of the present invention can be provided with a peelable protective film.
  • the protective film need not be provided on both surfaces of the translucent electromagnetic wave shielding film, and can be provided only on the conductive metal portion or on the opposite side. When the protective film is provided on a conductive metal part, V, it is desirable that it can be peeled off.
  • the peel strength of the protective film is preferably 5mNZ25mm width to 5NZ25mm width, more preferably 10mNZ25mm width to 100mNZ25mm width under the above test conditions. If it is less than the lower limit, peeling is too easy and the protective film may be peeled off during handling or inadvertent contact. If the upper limit is exceeded, a large force is required for peeling, and a conductive film is required for peeling. There is a risk that the conductive metal part may peel off from the support, which is not preferable.
  • polyethylene resin which is a polyolefin resin, polyester resin such as polypropylene resin, polyethylene terephthalate resin, polycarbonate resin, or resin film such as acrylic resin It is preferable to use, and the surface to which the protective film is bonded is preferably subjected to corona discharge treatment.
  • an acrylic ester-based, rubber-based, or silicone-based adhesive can be used.
  • the rolled translucent electromagnetic wave shielding film of the present invention and the optical film incorporating the same may be subjected to blackening treatment.
  • the black wrinkle process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576.
  • the blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antifungal effect.
  • the black layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil.
  • a chromate treatment may be performed thereon as a fouling treatment.
  • the chromate treatment is performed by immersing in a solution containing chromic acid or dichromate as a main component and drying to form an anti-fouling coating, which can be performed on one or both sides of the metal foil as required. Force Commercially available chromate-treated copper foil or the like may be used.
  • a metal foil that has been blackened in advance can be used, it may be blackened in an appropriate later step. Formation of the black wrinkle layer is accomplished by forming a photosensitive resin layer that can be a resist layer using a black colored composition, and leaving the resist layer without removal after etching is completed. Alternatively, a plating method that gives a black film may be used.
  • the configuration shown in Japanese Patent Application Laid-Open No. 11-266095 may be used. That is, after the first black layer is provided on the conductive metal portion and the electrolytic plating is performed on the first black layer, the second black layer is further formed on the plating. It is a configuration with layers. In order to perform electroplating on the first black layer, at least the first black layer must be conductive.
  • the conductive black layer can be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using an electrodepositing ionic polymer material such as an electrodeposition coating material.
  • the electrolyte bath containing the blackening material can be a black tanning bath containing nickel sulfate as a main component, and is also commercially available.
  • Blackish Attached bath can be used in the same way.
  • a black plating bath manufactured by Shimizu Corporation (trade name, Novroy SNC, Sn—Ni alloy system), black manufactured by Nippon Chemical Industry Co., Ltd.
  • Metal bath (trade name, Nitsuka black, Sn—Ni alloy), black bath bath (trade name, Evo-Chromium 85 series, 85 series, Cr series) manufactured by Metal Chemical Industry Co., Ltd. Can be used.
  • various black tanning baths such as Zn-based, Cu-based, and others can be used as the black tanning bath.
  • the conductive mesh is applied to form a conductive mesh pattern, and then a second black layer is formed thereon.
  • the metal with an electric field is Cu
  • treat the surface of Cu with hydrogen sulfide (HS) solution treatment.
  • HS hydrogen sulfide
  • the second black layer is formed.
  • the metal as the above-mentioned good conductive substance can be used as the most advantageous material. Therefore, when forming the above-mentioned metal electrodeposition layer, it is possible to use general-purpose metal electrolytes, so there are many types of inexpensive metal electrolytes, and it is free to choose the one that suits the purpose. There is an advantage that can be done. In general, Cu is frequently used as an inexpensive and highly conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are similarly used. It can be used for Next, in the present invention, the mesh-like conductive pattern 4 does not need to be composed of only a single metal layer.
  • the mesh-like conductive pattern 4 made of Cu in the above example is used. Since it is relatively soft and easily scratched, the protective layer can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr.
  • the blackening agent for the second blackening layer it can be easily manufactured using a sulfide-based compound, and there are many types of treating agents on the market. 'Copper black CuO, CuS, selenium-based Copa Black No. 65, etc. (made by Isolate Chemical Laboratories), trade name' Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used. Functional layers other than electromagnetic shielding of optical electromagnetic shielding film]
  • a functional layer having functionality may be separately provided as necessary.
  • This functional layer can have various specifications for each application.
  • display electromagnetic Wave shield materials include anti-reflective layers with anti-reflective functions that adjust the refractive index and film thickness, non-glare layers or anti-glare layers (both have anti-glare functions), and compounds and metals that absorb near-infrared rays.
  • Near-infrared absorption layer layer with a color tone adjustment function that absorbs visible light in a specific wavelength range
  • antifouling layer with a function that easily removes dirt such as fingerprints
  • hard-coat layer that is hard to scratch
  • impact A layer having an absorption function, a layer having a function of preventing glass scattering when the glass is broken, and the like can be provided.
  • These functional layers may be provided on the opposite side of the conductive metal part and the support, or may be provided on the same side.
  • a material provided with these functional layers is called an optical filter (or simply a filter).
  • each functional layer When using a translucent electromagnetic shielding film for a display (especially a plasma display), it is preferable to attach each functional layer by attaching a functional layer (functional film) described below.
  • the functional film can be directly or indirectly attached to the translucent electromagnetic shielding film via an adhesive or the like.
  • the functional film can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate. (Anti-reflective 'Anti-glare)
  • the translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, anti-glare properties (AG: anti-glare) properties to prevent reflection of mirror images, or both. It is preferable to provide any anti-glare and anti-glare (ARAG) function provided.
  • AR anti-reflection
  • AG anti-glare
  • the visible light reflectance is preferably 2% or less, more preferably 1.3% or less. More preferably, it is 0.8% or less.
  • a thin film of a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, silicon oxide, or the like is formed as a single layer with an optical film thickness of 1Z4 wavelength, for example.
  • Two or more thin films of inorganic compounds such as metal oxides, fluorides, halides, nitrides and sulfides, or organic compounds such as silicon-based resins, acrylic resins, and fluorine-based resins with different refractive indexes. It can be formed of a multi-layered laminate.
  • an antiglare layer 0.1 ⁇ ! It is possible to form a laminar force having a surface state with minute irregularities of about 10 m.
  • acrylic or silicone resin, melamine resin, urethane resin, alkyd resin, fluorinated resin, or other thermosetting or photocurable resin, silica, organic It can be formed by coating and curing an ink obtained by dispersing particles of an inorganic compound or organic compound such as a silicon compound, melamine, or acrylic.
  • the average particle size of the particles is preferably about 1 to 40 / ⁇ ⁇ .
  • the antiglare layer can also be formed by applying the thermosetting or photocurable resin as described above and then pressing and curing a mold having a desired dalos value or surface state. Monkey.
  • the haze generated during light transmission of the translucent electromagnetic shielding film is preferably 0.5% or more and 20% or less, more preferably 10% or less. % To 10%. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the transmitted image sharpness tends to be low.
  • the functional film has a hard coat property.
  • the hard coat layer include thermosetting type or photosetting type resin such as acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, and fluorine resin.
  • the type and formation method are not particularly limited.
  • the thickness of the hard coat layer is preferably about 1 to 50 / ⁇ ⁇ .
  • the surface hardness of the translucent electromagnetic shielding film with hard coat properties is JIS ( ⁇ -54
  • the pencil hardness according to (00) is preferably at least H, more preferably 2H, even more preferably 3H or more.
  • the transmissive electromagnetic wave shielding film has antistatic properties.
  • a film having high conductivity can be used.
  • the conductivity is about 10 11 ⁇ Zsq or less in terms of surface resistance
  • a highly conductive film can be formed by providing an antistatic layer on a transparent substrate.
  • the antistatic agent used in the antistatic layer include a trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), a trade name electroslipper (manufactured by Kao Corporation), and the like.
  • the antistatic layer may be formed of a known transparent conductive film such as ITO, or a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed.
  • the above hard coat layer, antireflection layer, antiglare layer and the like may be provided with antistatic properties by containing conductive fine particles.
  • the light-transmitting electromagnetic wave shielding film has antifouling property, it is preferable because it can be easily removed when it is prevented from being smudged or smudged.
  • a functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate.
  • a compound having antifouling property for example, a fluorine compound or a key compound may be used as long as the compound has non-wetting property with respect to water and Z or oil.
  • Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin) and the like, and examples of the key compound include trade name Takata Quantum (manufactured by NOF Corporation).
  • the functional film having ultraviolet cut-off property can be formed by a method in which an ultraviolet absorber is contained in the transparent substrate itself or by providing an ultraviolet absorbing layer on the transparent substrate.
  • the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less.
  • a functional film having an ultraviolet cutting property can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate.
  • Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their type 'concentration is dispersibility in the medium to be dispersed or dissolved' solubility, absorption wavelength-absorption coefficient, medium It is determined by the thickness of the material and is not particularly limited.
  • the functional film having ultraviolet cut-off property has little absorption in the visible light region and does not significantly reduce visible light transmittance or exhibit a color such as yellow. Moreover, when the layer containing the pigment
  • the translucent electromagnetic wave shielding film has a gas barrier property because it may be clouded or the adhesive may be phase-separated and deposited due to the influence of moisture.
  • the water vapor permeability of the functional film is preferably lOgZm 2 ⁇ day or less, preferably Is preferably 5 gZm 2 ⁇ day or less.
  • a plasma display Since a plasma display generates intense near-infrared rays, it is preferable to provide a near-infrared cut-off property, particularly when a light-transmitting electromagnetic wave shielding film is used for a plasma display.
  • a film having a transmittance of 25% or less in a wavelength region of 800 to 1 OOOnm is preferably less than 15%, more preferably less than 10%. is there.
  • the transmitted color is-neutral gray or blue gray. This is to maintain or improve the light emission characteristics and contrast of the plasma display, and is also a force that may prefer a white color temperature slightly higher than the standard white color.
  • color plasma displays are said to have insufficient color reproducibility.
  • the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm. There is a problem that red emission becomes poor in color purity close to orange due to a strong emission peak on the short wavelength side. Therefore, it is preferable that the functional film has a function of selectively reducing unnecessary light emission of the phosphor or discharge gas force that is the cause thereof.
  • optical properties can be controlled by using a dye.
  • near-infrared absorbers can be used for near-infrared cut, and dyes that selectively absorb unwanted luminescence can be used to reduce unwanted luminescence.
  • the color tone can also be made suitable by using a dye having an appropriate absorption in the visible region.
  • the dye may be a general dye or pigment having a desired absorption wavelength in the visible region, or a compound known as a near-infrared absorber, and the type thereof is not particularly limited.
  • a compound known as a near-infrared absorber for example, anthraquinone, phthalocyanine, methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene
  • organic dyes that are generally commercially available, such as pyromethene-based compounds, dithiol-based compounds, and diiminium-based compounds.
  • the plasma display has a heat resistance that does not deteriorate at about 80 ° C, for example, because the temperature of the translucent electromagnetic wave shielding film increases when the temperature of the environment where the panel surface temperature is high is high. It is preferable to speak.
  • some dyes have poor light resistance. If such dyes cause problems with the light emission of plasma displays and the deterioration of UV light and visible light from outside light, functional films as described above. It is preferable to prevent the dye from being deteriorated by ultraviolet rays or visible rays by adding an ultraviolet absorber to the layer or providing a layer that does not transmit ultraviolet rays.
  • the transmission characteristics of the optical filter change, and the color tone may change or the near-infrared cutting ability may decrease.
  • the dye is highly soluble and dispersible in the solvent in order to dissolve or disperse it in the resin composition for forming the transparent substrate and the coating composition for forming the coating layer. Is preferred.
  • the concentration of the dye is appropriately set based on the absorption wavelength of the dye, the absorption coefficient, the transmission characteristics required for the translucent electromagnetic wave shielding film, the transmittance, and the type of the medium or coating film to be dispersed. can do.
  • the functional film When the functional film contains a pigment, it may be contained inside the transparent substrate, or a layer containing the pigment may be coated on the surface of the substrate. Further, two or more kinds of dyes having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing dyes may be provided.
  • the functional film containing the dye has a layer containing the light transmitting electromagnetic wave shield. More preferably, it is arranged so that it does not come into contact with the conductive metal part on the metal film.
  • the translucent electromagnetic shielding film with the functional film attached is attached to the display, it is usually attached so that the functional film is on the outside and the adhesive layer is on the display side.
  • the conducting part is preferably provided around the conductive metal part along the peripheral edge of the translucent electromagnetic wave shielding film.
  • the conductive portion may be formed of a mesh pattern, or may be patterned! /,
  • the conductive portion may be formed of a mesh pattern, or may be patterned! /,
  • the metal foil is not patterned like a solid metal foil.
  • the conductive part may be a mesh pattern layer or not patterned, for example, a solid layer of metal foil, the electrical connection with the ground part of the display body is good.
  • the conductive portion be patterned like a metal foil solid layer.
  • the conductive part is not patterned like a solid metal foil, and when Z or the mechanical strength of the conductive part is sufficiently strong, the conductive part itself can be used as an electrode. It is.
  • an electrode on the conducting part it is preferable to form an electrode on the conducting part to protect the conducting part and to make good electrical contact with the grounding part when Z or the conducting part is a mesh pattern layer.
  • the shape of the electrode is not particularly limited, but it is preferable that the electrode is formed so as to cover all the conductive portions.
  • the material used for the electrode is composed of a single substance or two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. in terms of conductivity, contact resistance and adhesion to the transparent conductive film.
  • An alloy, a synthetic resin and a single substance or a mixture of these alloys, or a paste that also has a mixture force between a borosilicate glass and these single substances or an alloy can be used. Conventionally known methods can be employed for printing and coating the paste.
  • Commercially available conductive tape can also be suitably used.
  • the conductive tape is conductive on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used.
  • the thickness of the electrode is also not particularly limited, but is about several / zm to several mm.
  • an optical filter having excellent optical characteristics that can maintain or improve the image quality without significantly impairing the luminance of the plasma display.
  • it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health of the plasma display, and near infrared rays near 800 to 1000 nm are also emitted from the plasma display. Therefore, it is possible to obtain an optical filter that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof.
  • an optical filter having excellent weather resistance can be provided at a low cost.
  • Hexaclo oral rhodate ammonium (0.001% NaCl 20% aqueous solution) 7ml Potassium hexaloiridium (III) (0.005% KC1 20% aqueous solution) and hexachloro oral rhodate ammonium 0.001% NaC120% aqueous solution) was prepared by dissolving the powder in KC1 20% aqueous solution and NaC120% aqueous solution, respectively, and heating at 40 ° C. for 120 minutes.
  • Sample 1-1 was prepared by coating on a polyethylene terephthalate film support consisting of a moisture-proof undercoat containing both sides of the polyvinylidene chloride shown below so as to form the UL layer Z emulsion layer.
  • the preparation method, coating amount and coating method of each layer are shown below.
  • sensitizing dye (sd-1) 5.7 X 10- 4 mole Z mol Ag to the emulsion A. Further to KBr3.4 X 10- 4 mole Z mol Ag, the compound (Cpd- 3) 8.0 X 10- 4 mole Z mol Ag Karoe, and mixed well.
  • Polyethylene terephthalate resin having an inherent viscosity of 0.66 which was polycondensed using antimony trioxide and antimony as the main catalyst, was dried to a water content of 50 ppm or less and melted in an extruder set at a heater temperature of 280 to 300 ° C.
  • the molten PET resin is discharged from a die part onto a chill roll that is electrostatically applied to obtain a non-crystalline base.
  • the obtained amorphous base was stretched 3.1 times in the direction of base travel and then 3.9 times in the width direction to produce a 96 m thick support in roll form.
  • a coating solution having the following composition was successively applied and dried under the following coating conditions to form the following back layer (easy adhesion layer).
  • the surface of the support was subjected to corona discharge treatment under printing energy 727 jZm 2 conditions, and then the antistatic layer having the following compositional power.
  • the use coating liquid application amount was applied by bar coating method at 7. lccZm 2.
  • an antistatic layer was obtained by drying at 180 ° C. for 1 minute in an air flotation drying zone.
  • Polyacrylic resin Jiurimer ET-410: Nippon Pure Chemical Co., Ltd., solid content 30%
  • Needle-shaped tin oxide particles F-10D: Ishihara Sangyo Co., Ltd., solid content 20%
  • 131.1 parts by mass Carposiimide compound Carposiimide compound (Carpolite V-02- L2: Nisshinbo, solid content 40%)
  • Surfactant Sandet BL: Sanyo Chemical Industries solid content 44.6%)
  • Silica fine particle dispersion Seahoster KE-W30: Nippon Shokubai 0.3 ⁇ m solids 20%
  • a coating solution for the surface layer having the following composition was applied on the antistatic layer at a coating amount of 5.05 ccZm 2 by the bar coating method. Subsequently, a back layer having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.
  • An undercoat coating solution having the following composition was simultaneously applied to the surface of the polyethylene terephthalate support opposite to the surface on which the back layer was formed, thereby forming an undercoat layer for the emulsion layer. That is, in the state where the substrate was conveyed at a conveyance speed of 105 mZ, the opposite surface of the support was subjected to corona discharge treatment under 467 jZm 2 conditions, and the coating solution for the first subbing layer having the following composition was applied by the bar coating method. It applied by. The coating amount was 5.05 ccZm 2, and the first undercoat layer was obtained by drying at 180 ° C. for 1 minute in the air flotation drying zone, the same as the back layer antistatic layer drying zone.
  • Polystyrene fine particles (average particle size 2 ⁇ )
  • a coating solution having the following composition was subsequently applied onto the first undercoat layer by the bar coating method.
  • the coating amount was 8.7 cc / m 2
  • a second undercoat layer was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.
  • the obtained Sample 11 had an applied silver amount of 7.6 g / m 2 , an Ag / gelatin mass ratio of the emulsion layer of 6.9, a swelling ratio of 209%, and a product of Ag / gelatin mass ratio and swelling ratio of 13.2. It was a photosensitive material having an emulsion layer as the uppermost layer.
  • the swelling ratio of the emulsion layer was determined as follows. That is, by observing a section of the dried sample with a scanning electron microscope, the thickness (a) of the emulsion layer at the time of drying is obtained, immersed in distilled water at 25 ° C for 1 minute, and then freeze-dried with liquid nitrogen. By observing the slice of the sample with a scanning electron microscope, the film thickness (b) of the emulsion layer during swelling was determined, and the swelling ratio was calculated by the following equation.
  • the exposed sample was subsequently subjected to development processing to create a metallic silver part.
  • Electrolytic plating 2 35 ° C 30 seconds
  • the water washing process was a two-tank counter-flow system with two rinses, 1, four rinses, and three rinses from 6 to 5.
  • composition of each treatment solution is as follows.
  • Electrolytic copper plating solution composition (same replenisher composition)
  • the oxidation-reduction potential of the black-and-white developer was 340 mVvs SCE, expressed as the bath potential obtained by immersing the rotating platinum electrode in the developer.
  • samples shown in Table 1 were prepared by changing the amount of gelatin (Gel) used in the binder of the emulsion. Samples that were not plated, samples that were reduced after development, and samples that were calendered were prepared.
  • Gel gelatin
  • the reduction treatment was performed by treatment with a 0.01 mol / L aqueous solution of sodium triacetoxyborohydride for 5 minutes.
  • the calendering process was performed by applying a linear pressure of 2940 N / cm (300 kg / cm) with a calender roll and passing the sample between calender rollers with two pairs of metal roll forces.
  • each sample was subjected to the exposure and development processes described above, so that the conductive metal portion and the metal were substantially present.
  • a light-transmitting electromagnetic wave shielding film was formed as a light transmitting part.
  • the conductive metal part exhibited a mesh pattern corresponding to the exposure pattern, and the line Z space width was 15 ⁇ m / 285 ⁇ m in all samples. In all samples, the aperture ratio of the light transmission part was about 90%.
  • Each sample is developed without being exposed! ⁇ The surface of each sample was visually observed to evaluate whether or not a black spot-like or linear developed silver was formed.
  • the evaluation criteria were as follows.
  • Level A 0 to 3 black spots or linear developed silver.
  • Level B 4 to 10 black spots or linear developed silver.
  • Level C Number of black spots or linear developed silver is 10 or more.
  • Revenore A Number of breaks 0 to: LO.
  • Level B Number of breaks 11 or more.
  • Level C Number of disconnections 20 or more.
  • Example 1 A glass plate was bonded to the inner light-transmitting electromagnetic wave shielding film excluding the outer edge portion of 20 mm through an acrylic light-transmitting adhesive material having a thickness of 25 m.
  • the acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the optical filter.
  • an anti-reflection film having a near-infrared cutting ability (trade name Realic 7 72UV manufactured by Nippon Oil & Fats Co., Ltd.) was bonded to the opposite main surface of the glass plate via an adhesive material to produce an optical filter. .
  • the display image does not take on a metallic color, and has an electromagnetic wave shielding ability and a near infrared ray cutting ability that are not problematic in practice, and an antireflection film. It was excellent in visibility.
  • a pigment it has been possible to impart a color-adjusting function, and it can be suitably used as an optical filter for plasma displays and the like.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract

La présente invention concerne un film de protection électromagnétique transmettant la lumière à faible coût et montrant une excellente productivité et de grandes performances de protection électromagnétique, sans générer de brouillard. L'invention concerne également un filtre optique et un écran plasma utilisant ce film. Elle concerne précisément un procédé pour produire un film conducteur, qui comprend une étape de développement au cours de laquelle une partie de métal d'argent est formée en exposant et en développant un film photosensible ayant une couche d'émulsion de sel d'agent sur un support, une étape de réduction au cours de laquelle un agent de réduction est amené au contact de la surface de la partie de métal d'argent, ainsi qu'une étape de lissage au cours de laquelle le film photosensible réduit est soumis à un lissage. L'invention concerne aussi précisément un film de protection électromagnétique transmettant la lumière, un filtre optique et un écran plasma produit à l'aide de ce film conducteur.
PCT/JP2007/051613 2006-01-31 2007-01-31 Procede de production de film conducteur, film de protection electromagnetique transmettant la lumiere, filtre optique et ecran plasma WO2007088896A1 (fr)

Applications Claiming Priority (2)

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JP2006-022948 2006-01-31
JP2006022948 2006-01-31

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WO2007088896A1 true WO2007088896A1 (fr) 2007-08-09

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WO (1) WO2007088896A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251417A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp 導電膜及びその製造方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
JPH11145676A (ja) * 1997-11-11 1999-05-28 Hitachi Chem Co Ltd 電磁波シールド性接着フィルムおよび該接着フィルムを用いた電磁波遮蔽構成体、ディスプレイ
JP2004039981A (ja) * 2002-07-05 2004-02-05 Hitachi Chem Co Ltd Ｅｍｉシールドフィルム及びその製造方法
JP2004221565A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜およびその製造方法
JP2004296990A (ja) * 2003-03-28 2004-10-21 Dainippon Printing Co Ltd 電磁波遮蔽シート、およびその製造方法
WO2005115070A1 (fr) * 2004-05-24 2005-12-01 Gunze Limited Matériau de protection d'onde électromagnétique et son processus de production
JP2006012935A (ja) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法および透光性電磁波シールド膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11145676A (ja) * 1997-11-11 1999-05-28 Hitachi Chem Co Ltd 電磁波シールド性接着フィルムおよび該接着フィルムを用いた電磁波遮蔽構成体、ディスプレイ
JP2004039981A (ja) * 2002-07-05 2004-02-05 Hitachi Chem Co Ltd Ｅｍｉシールドフィルム及びその製造方法
JP2004221565A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜およびその製造方法
JP2004296990A (ja) * 2003-03-28 2004-10-21 Dainippon Printing Co Ltd 電磁波遮蔽シート、およびその製造方法
WO2005115070A1 (fr) * 2004-05-24 2005-12-01 Gunze Limited Matériau de protection d'onde électromagnétique et son processus de production
JP2006012935A (ja) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法および透光性電磁波シールド膜

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251417A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp 導電膜及びその製造方法
WO2008123437A1 (fr) * 2007-03-30 2008-10-16 Fujifilm Corporation Film conducteur et son procédé de fabrication
US8071271B2 (en) 2007-03-30 2011-12-06 Fujifilm Corporation Conductive film and method for producing the same

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